Methods to produce zeolites with the GME topology and compositions derived therefrom

ABSTRACT

The present disclosure is directed to microporous crystalline aluminosilicate structures with GME topologies having pores containing organic structure directing agents (OSDAs) comprising at least one piperidinium cation, the compositions useful for making these structures, and methods of using these structures. In some embodiments, the crystalline zeolite structures have a molar ratio of Si:Al that is greater than 3.5.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application to U.S. patent applicationSer. No. 15/864,392, filed Jan. 8, 2018, which is a divisionalapplication to U.S. patent application Ser. No. 15/050,839, filed Feb.23, 2016, which issued as U.S. Pat. No. 9,878,312 on Jan. 30, 2018,which itself claims priority to U.S. Patent Application Ser. No.62/119,945 filed Feb. 24, 2015 and U.S. Patent Application Ser. No.62/133,074 filed Mar. 13, 2015, the contents of all of which areincorporated by reference herein in their entireties for all purposes.

TECHNICAL FIELD

The present disclosure is directed to producing zeolite structures withGME topologies using organic structure directing agents (OSDAs), and thecompositions and structures resulting from these methods.

BACKGROUND

The GME topology describes a microporous molecular sieve having 1D12-membered ring (MR) channels intersected by 8 MR channels in 2dimensions. Its 3D channel (12×8×8) system with pore sizes of 7.11×7.11Å (12MR) and 3.41×3.41 Å (8MR), respectively, can include spheres up to7.76 Å. This framework was first recognized in the natural occurringaluminosilicate (zeolite) mineral gmelinite. Since then, routes towardssynthetic GME have been explored. Two notable paths are known from theliterature: one using cationic (DABCO) polymeric templates inconjunction with a silica sol and sodium aluminate as respective Si andAl sources, and one based on the hydrothermal conversion of zeolite Y(FAU) in presence of Sr²⁺ cations. However, most materials, andespecially the natural occurring gmelinite, are faulted (containingcrystallographic errors in the structure, possible causing obstructionsof channels etc.) and therefore possess rather low sorption capacities.When exchanged with sodium, nitrogen adsorption capacities, as measuredby N₂-physisorption at −196° C., were reported to be nearly 0 cm³·g⁻¹for natural Na-GME and respectively 0.055 cm³·g⁻¹ and 0.031 cm³·g⁻¹ forthe DABCO-GME and the GME made by converting FAU. This, together withstreaking in electron diffraction indicated that these samples are allhighly faulted. It is moreover known that this can be caused by anintergrowth of chabazite (framework topology CHA). The degree offaulting (although present in lesser extent in the DABCO-GME) largelydetermines the sorption capacity as it blocks the large 12MR channels.

It would be desirable to find a synthetic route to GME with an organicstructure directing agent (SDA), that prevents CHA intergrowth andstacking faults and in general, it would be desirable to find a routewith a simpler SDA, as the ‘polymeric DABCO’ OSDA is hard to obtain. Itwould be also be beneficial to find a synthetic route towards GME withSi/Al values above 3.5, since this parameter largely influences thesorption and catalytic properties and the (hydrothermal) stability ofthe framework.

The present invention is directed to addressing at least some of theshortcomings of the existing art.

SUMMARY

The present invention is directed to the use of quaternary piperidiniumsalts to prepare zeolites having GME topologies, and the novel materialsderived from these processes.

The disclosure provided certain embodiments directed to processes ofmaking zeolite compositions of a GME topology, each process comprisinghydrothermally treating an aqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a mineralizing agent; and

(d) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporoussolid of GME topology;wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In certain aspects of this disclosure, the process is done in theabsence of the sources of aluminum oxide, boron oxide, gallium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, zirconium oxide, or combination or mixture thereof. Inother embodiments, the process comprises hydrothermal treating of anaqueous composition comprising (a) a source of a silicon oxide; (b) asource of aluminum oxide; (c) mineralizing agent, preferably ahydroxide; and (d) the organic structure directing agent (OSDA) ofFormula (I).

The quaternary piperidinium cation of Formula (I) is also defined invarious embodiments in terms of sub-genera and specific quaternarypiperidinium cations. For example, in some embodiments, the quaternarypiperidinium cation is defined in terms of:

(a) structures of Formula (IA) or (IB):

(b) certain N,N-dialkyl-2,6-lupetidinium cations or anN,N-dialkyl-3,5-lupetidinium cations:

(c) cis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof; and

(d) cis-N,N-dimethyl-3,5-lupetidinium cation,trans-N,N-dimethyl-3,5-lupetidinium cation,cis-N,N-dimethyl-2,6-lupetidinium cation,trans-N,N-dimethyl-2,6-lupetidinium cation or a combination thereof.

In general, the quaternary 3,5 piperidinium cations, or mixturescomprising these cations are preferred, particularly,cis-N,N-dialkyl-3,5-lupetidinium cation, orcis-N,N-dimethyl-3,5-lupetidinium cation, of mixtures comprising thesecations.

The nature of the sources of the various oxides and their ratio ranges,the nature of the mineralizing agent, and the hydrothermal heatingconditions are also disclosed as separate embodiments.

In some embodiments, the processes further comprise isolating thecrystalline microporous solid of GME topology and on some cases, furtherprocessing the isolated crystalline solids. These processes includeprocess steps to remove at least a portion and preferably substantiallyall of the OSDA occluded in the pores of the isolated solids. In someembodiments, this further processing is done in the presence of analkali, alkaline earth, transition metal, rare earth metal, ammonium oralkylammonium salts (anions including halide, preferable chloride,nitrate, sulfate, phosphate, carboxylate, or mixtures thereof) to form adehydrated or an OSDA-depleted product. In other embodiments, thefurther processing is done in the absence of such salts. In otheraspects, these salts are added in a separate step from the removal ofthe OSDA.

These compositions typically include analogous embodiments as describedfor the process that more specifically define the nature of the OSDA,the ratios of the various components, and the processing conditions.Still other embodiments provide for crystalline microporous solidshaving pores at least some of which are occluded with at least oneisomer of the quaternary piperidinium cation of Formula (I).

The products of the hydrothermal treating may be isolated and subjectedto one or more of further processing conditions. Such treatmentsinclude:

(a) contacting the isolated crystalline microporous solid with ozone orother oxidizing agent at a temperature in a range of 100° C. to 200° C.;and

(b) heating the isolated crystalline microporous solid at a temperaturein a range of from about 200° C. to about 600° C. in either the absenceor presence of an alkali, alkaline earth, transition metal, rare earthmetal, ammonium or alkylammonium salts;

in each case for a time sufficient to form a dehydrated or anOSDA-depleted crystalline microporous product. Certain sub-embodimentsdescribe specific aspects of these treatments.

These dehydrated or OSDA-depleted crystalline microporous products maybe further treated with an aqueous ammonium or metal cation salt and/orwith at least one type of transition metal or transition metal oxide.

Various embodiments disclose the compositions prepared by any one of theprocesses embodiments. These include compositions which may be describedas:

(a) compositions comprising the aqueous compositions used in thehydrothermal treatments together with a compositionally consistentcrystalline microporous aluminosilicate product, the compositionallyconsistent crystalline microporous products containing the OSDA used intheir preparation occluded in their pores;

(b) the isolated crystalline microporous products which contain the ofFormula (I) occluded in their pores; and

(c) the crystalline microporous products which have been dehydrated orfrom which the OSDAs have been substantially depleted from their poresand/or which have been post-treated to add salts, metals, or metaloxides into the pores of the crystalline microporous products.

While these compositions have been described and claimed in terms of theprocesses used to prepare them, other embodiments describe and claimthese compositions in terms which do not require these processlimitations. For example, certain embodiments disclose compositions ofcrystalline microporous solids of GME topology, described in terms ofthe ratios of the respective components. For example, in certainembodiments, the crystalline microporous solids, whether containing theOSDA or not, have molar ratio of Si:Al of from greater than 3.5 to about15 (or SiO₂/Al₂O₃ ratio greater than 7 to about 30). Independentembodiments provide subsets of these ranges.

In other embodiments, the crystalline microporous solids are describedin terms of certain physical characteristics of the aluminosilicatesolids, for example with respect to XRD patterns, ²⁹Si MAS NMR spectra,²⁷Al MAS NMR spectra, N₂ or argon physisorption isotherms, andthermogravimetric analysis (TGA) data.

Still other embodiments include those which use the disclosecompositions in an array of catalytic processes.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods of making and methods of using,processes, devices, and systems disclosed. In addition, the drawings arenot necessarily drawn to scale. In the drawings:

FIG. 1 shows the DABCO polymer, previously the only known OSDA forsynthetic GME zeolite synthesis.

FIG. 2 shows a structure of quaternizedN,N-dimethyl-3,5-dimethylpiperidine, one of the OSDAs of the instantdisclosure.

FIG. 3 shows PXRD traces of CIT-9 (GME) produced in different gelsaccording to Table 1. *ANA impurity; ^(•)ANA impurity combined with aGME reflection.

FIG. 4 shows thermogravimetric analysis curves derived from an as-madeCIT-9 from Table 1, entry 1: MDU80

FIG. 5 shows ¹³C CP MAS NMR spectra of as-made MDU190 (upper trace) andthe OSDA tetramethyl-N,N,3,5-piperidinium hydroxide (lower trace) (500MHz).

FIG. 6 shows PXRD traces of CIT-9 produced in synthesis MDU80: as made;after ozone-treatment; after ozone-treatment and subsequent NW-exchange.

FIG. 7 shows PXRD traces of CIT-9 produced in synthesis MDU93: as made;after ozone-treatment; after ozone and subsequent K⁺-exchange; afterozone, K⁺-exchange and calcination at 580° C.

FIG. 8 shows SEM images of as-made CIT-9 produced in Table 1 entry 1:MDU80. 30,000× magnification. Bar=1 micron

FIG. 9 shows SEM images of CIT-9 produced in Table 1 entry 2: MDU93.Upper: As-made material (16,030× magnification, Bar=1 micron); Bottom:After ozone-treatment, K⁺-exchange and calcination at 580° C. (12,300×magnification, Bar=2 micron).

FIG. 10 shows a physisorption isotherm for MDU53 with N₂-gas and MDU80with Argon after treatment with ozone at 150° C. for removal of the SDA.

FIG. 11 shows an ²⁷Al MAS NMR spectrum for MDU93 after ozone treatment,K-exchange and calcination. (300 MHz)

FIG. 12 shows ²⁹Si MAS (Bloch Decay) NMR spectra for MDU93 afterozone-treatment, K-exchange and calcination. (500 MHz).

FIG. 13 shows PXRD patterns of as-made CIT-9, CIT-9 after calcinationand CIT-9 after calcination in the presence of salt.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to methods of producing crystallinealuminosilicate molecular sieves with the GME topology using quaternarypiperidine OSDAs and the corresponding compositions. Additionally, newGME aluminosilicate compositions, called CIT-9, are disclosed, withmolar ratios of Si:Al that are greater than 3.5. The new synthesisroutes give access to GME zeolites with pore volumes over 0.1 cm³/g.

The only successful OSDA reported so far in the preparation of GMEmaterials is the DABCO polymer, structurally illustrated in FIG. 1 .Moreover, all synthetic GMEs prepared so far have a molar ratio of Si:Alratio in the range of from 2.0-3.5. GME with Si:Al ratios above 3.5 aredesirable, since this ratio largely influences the sorption andcatalytic properties and the (hydrothermal) stability of the framework.

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, processes, conditions or parameters described or shown herein,and that the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe invention herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this specification, claims, anddrawings, it is recognized that the descriptions refer to compositionsand processes of making and using said compositions. That is, where thedisclosure describes or claims a feature or embodiment associated with acomposition or a method of making or using a composition, it isappreciated that such a description or claim is intended to extend thesefeatures or embodiment to embodiments in each of these contexts (i.e.,compositions, methods of making, and methods of using).

Terms

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method or process steps; (ii) “consisting of” excludes anyelement, step, or ingredient not specified in the claim; and (iii)“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention. Embodimentsdescribed in terms of the phrase “comprising” (or its equivalents), alsoprovide, as embodiments, those which are independently described interms of “consisting of” and “consisting essentially of” For thoseembodiments provided in terms of “consisting essentially of” the basicand novel characteristic(s) of a process is the ability to provide thenamed GME compositions using the named OSDAs under conditions favoringthe stabile formation of the GME compositions, without the necessaryneed for other ingredients, even if other such components are present.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are described herein.

Unless otherwise stated, ratios or percentages are intended to refer tomole percent or atom percent, as appropriate.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

The terms “oxygenated hydrocarbons” or “oxygenates” as known in the artof hydrocarbon processing to refer to components which include alcohols,aldehydes, carboxylic acids, ethers, and/or ketones which are known tobe present in hydrocarbon streams or biomass streams from other sources(e.g., ethanol from fermenting sugar).

The terms “separating” or “separated” carry their ordinary meaning aswould be understood by the skilled artisan, insofar as they connotephysically partitioning or isolating the product material from otherstarting materials or co-products or side-products (impurities)associated with the reaction conditions yielding the material. As such,it infers that the skilled artisan at least recognizes the existence ofthe product and takes specific action to separate or isolate it fromstarting materials and/or side- or byproducts. Absolute purity is notrequired, though it is preferred.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of at leastsolvents or other impurities, such as starting materials, co-products,or byproducts. In some embodiments, the isolated crystalline materials,for example, may be considered isolated when separated from the reactionmixture giving rise to their preparation, from mixed phase co-products,or both. In some of these embodiments, for example, purealuminosilicates (or structures containing incorporated OSDAs) can bemade directly from the described methods. In some cases, it may not bepossible to separate crystalline phases from one another, in which case,the term “isolated” can refer to separation from their sourcecompositions.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesembodiments where the circumstance occurs and instances where it doesnot. For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present. Similarly, the phrase “optionally isolated” means thatthe target material may or may not be separated from other materialsused or generated in the method, and, thus, the description includesseparate embodiments where the target molecule or other material isseparated and where the target material is not separated, such thatsubsequence steps are conducted on isolated or in situ generatedproduct.

The terms “method(s)” and “process(es)” are considered interchangeablewithin this disclosure.

As used herein, the term “crystalline microporous solids” or“crystalline microporous silicate or aluminosilicate solids,” sometimesreferred to as “molecular sieves,” are crystalline structures havingvery regular pore structures of molecular dimensions, i.e., under 2 nm.The term “molecular sieve” refers to the ability of the material toselectively sort molecules based primarily on a size exclusion process.The maximum size of the species that can enter the pores of acrystalline microporous solid is controlled by the dimensions of thechannels. These are conventionally defined by the ring size of theaperture, where, for example, the term “8-MR” or “8-membered ring”refers to a closed loop that is typically built from eight tetrahedrallycoordinated silicon (or aluminum) atoms and 8 oxygen atoms. These ringsare not necessarily symmetrical, due to a variety of effects includingstrain induced by the bonding between units that are needed to producethe overall structure, or coordination of some of the oxygen atoms ofthe rings to cations within the structure. The term “silicate” refers toany composition including silicate (or silicon oxide) within itsframework. It is a general term encompassing, for example, pure-silicate(i.e., absent other detectable metal oxides within the framework),aluminosilicate, borosilicate, or titanosilicate structures. The term“aluminosilicate” refers to any composition including silicon andaluminum oxides within its framework. In some cases, either of theseoxides may be substituted with other oxides. “Pure aluminosilicates” arethose structures having no detectable other metal oxides in theframework. As long as the framework contains silicon and aluminumoxides, these substituted derivatives fall under the umbrella ofaluminosilicates. The term “zeolite” also refers to an aluminosilicatecomposition that is a member of this family. When described as“optionally substituted,” the zeolite framework may contain boron,gallium, hafnium, iron, tin, titanium, indium, vanadium, or zirconiumatoms substituted for one or more aluminum or silicon atoms in theframework. As described elsewhere, the GME topology describes amicroporous molecular sieve having 1D 12-membered ring (MR) channelsintersected by 8 MR channels in 2 dimensions. Its 3D channel (12×8×8)system with pore sizes of 7.11×7.11 Å (12MR) and 3.41×3.41 Å (8MR),respectively, can include spheres up to 7.76 Å.

The material described herein as “CIT-9” refers to an crystallinemicroporous aluminosilicate material having a structure characteristicsthe same as a material produced by the OSDA route described herein, inwhich the OSDA comprises a cis-N,N-dimethyl-3,5-lupetidinium cation.

The present disclosure describes and is intended to lay claim to methodsof making crystalline compositions, the compositions themselves, andmethods of using the crystalline aluminosilicate compositions having aGME framework. As described elsewhere as well, it should be appreciatedthat any embodied feature described for one of these categories (i.e.,compositions and methods of making or using) is applicable to all othercategories.

Processes of Preparing Crystalline Compositions

Certain embodiments involve those process for preparing analuminosilicate composition having a GME topology, each processcomprising hydrothermally treating an aqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a mineralizing agent; and

(d) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporousaluminosilicate solid of GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

The counterion to the cationic organic structure directing agent mixturein Formula (I) is generally a bromide, chloride, fluoride, iodide, orhydroxide ion, but the OSDA may be added also to the composition as anacetate, nitrate, or sulfate. In some embodiments, the quaternarypiperidinium cation has an associated fluoride or hydroxide ionpreferably substantially free of other halide counterions. In separateembodiments, the associated anion is hydroxide.

It should be appreciated that the instant invention provides that thequaternary piperidinium cation may comprise one or more stereoisomers ofthe same structural compound or two or more different compounds,selected from these options. For the sake of brevity, reference to anisomer by individual digits is intended to refer to that isomersubstituted in that position. For example, the “2,6 isomer” refers to anisomer containing an alkyl substituent only in the R² and R⁶ positions;a “3,5 isomer” refers to an isomer containing an alkyl substituent onlyin the R³ and R⁵ positions.

Reference to “isomers” in Formula (I) (and Formula (IA) and (IB)discussed elsewhere) refers to both structural and stereochemicalisomers of the quaternary piperidinium cation. That is, reference to twoor more isomers may encompass multiple structural isomers (e.g.,individual mono-alkyl compounds substituted in the 2, 3, 4, 5, or 6positions, or di-alkyl compounds substituted in the 2,3 and 2,4 and 2,5and 2,6, and 3,4 and 3,5, and 4,5 positions, or combinations thereof).In some cases, these may include mixtures of homologs (e.g., where R² ismethyl and R⁶ is ethyl), stereoisomers of the same structural isomer(e.g., cis-2-methyl/6-methyl and trans-2-methyl/6-methyl), orcombinations of both (e.g., cis-3-methyl/5-methyl andtrans-3-methyl/5-ethyl).

For example, referring to the structure of Formula (I), options for thequaternary piperidinium cations include those where R², R³, R⁴, R⁵, andR⁶ are individually and independently methyl, ethyl, n-propyl, oriso-propyl, independent of stereochemistry. In separate embodiments, thecarbon skeleton of piperidinium cation may be di-, tri-, tetra-, orpenta-substituted with any of these C₁₋₃ alkyl groups, independent ofstereochemistry.

The piperidine frameworks which derive the quaternary piperidiniumcations may be conveniently derived from the products of hydrogenationof di-, tri, or tetraalkyl pyridine precursors, via the intermediaryformation of the corresponding di-, tri, or tetraalkyl piperidiniumprecursors, for example using Pt/H₂ or Raney Nickel catalysts. Given theavailability of such pyridine precursors, in some embodiments, dialkylpiperidinium frameworks are conveniently obtained by such processes,especially, for example, where R³ and R⁵ are alkyl, preferably ethyl ormethyl, more preferably methyl or where R² and R⁶ are alkyl, preferablyethyl or methyl, more preferably methyl. In the former case, where R³and R⁵ are methyl and R², R⁴, and R⁶ are H, the structures are known as3,5-lupetidinium cations. In the latter case, where R² and R⁶ are methyland R³, R⁴, and R⁵ are H, the structures are known as 2,6-lupetidiniumcations.

R^(A) and R^(B) are defined as being independently a C₁₋₃ alkyl, ortogether with the N to which they are bound form a 5 or 6 memberedsaturated or unsaturated ring. As such, in some embodiments, R^(A) andR^(B) are independently methyl, ethyl, n-propyl, or iso-propyl. In otherembodiments, R^(A) and R^(B), together with the N to which they arebound, form a 5 or 6 membered saturated or unsaturated ring. Forexample, these may include structures described as a spiro-pyrrolidiniummoiety, also described as a 5-azonia-spiro [4,5] decane:

or a spiro-piperidinium moiety, also described as a 6-azonia-spiro [4,5]undecane:

or a spiro-2,5-dihydro-1H-pyrrolium moiety, also described as a5-azonia-spiro [4,5] dec-2-ene:

Again, in certain embodiments of these structures, the 2,6 positions(i.e., R² and R⁶) are alkyl, preferably ethyl or methyl, more preferablymethyl, the remaining positions being H. In other embodiments, the 3,5positions (i.e., R³ and R⁵) are alkyl, preferably ethyl or methyl, morepreferably methyl, the remaining positions being H.

In some embodiments, the OSDA used in these processes comprises at leastone isomer of the quaternary piperidinium cation of Formula (IA) or(IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some embodiments, the quaternary piperidinium cation of Formula (I)is or comprises an N,N-dialkyl-2,6-lupetidinium cation or anN,N-dialkyl-3,5-lupetidinium cation:

where R^(A) and R^(B) are C₁₋₃ alkyl, preferable methyl. In separateindependent embodiments, the quaternary piperidinium cation of Formula(I) is or comprises an N,N-dialkyl-2,6-lupetidinium cation or anN,N-dialkyl-3,5-lupetidinium cation.

In related embodiments, the quaternary piperidinium cation of Formula(I) is an N,N-dimethyl-3,5-lupetidinium cation,N,N-dimethyl-2,6-lupetidinium cation, N,N-diethyl-3,5-lupetidiniumcation, N,N-diethyl-2,6-lupetidinium cation, a6,10-dimethyl-5-azonia-spiro[4.5]decane, a1,5-dimethyl-6-azonia-spiro[5.5]undecane, a7,9-dimethyl-5-azonia-spiro[4.5]decane, a2,4-dimethyl-6-azonia-spiro[5.5]undecane, or a combination thereof.

Still further embodiments include those where the quaternarypiperidinium cation of Formula (I) is or comprisescis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Including those wherein R^(A)′ and R^(B) are both methyl.

In other embodiments, the quaternary piperidinium cation of Formula (I)comprise a mixture of cis-N,N-dimethyl-3,5-lupetidinium cation andtrans-N,N-dimethyl-3,5-lupetidinium cation, a mixture ofcis-N,N-dimethyl-2,6-lupetidinium cation andcis-N,N-dimethyl-3,5-lupetidinium cation, or a combination thereof.

In some embodiments, the ratios of cis and trans in these di-substitutedmaterials may range from about 99% cis/1% trans to about 0% cis/100%trans. In other embodiments, the at least two isomers of the quaternarypiperidinium cation of Formula (I) comprise a mixture ofcis-N,N-dimethyl-3,5-lupetidinium cation andtrans-N,N-dimethyl-3,5-lupetidinium cation in a mole ratio of about 99%cis/1% trans to about 0% cis/100% trans. Other embodiments provide thatthese ratios range from about 98:2 to 95:5, from about 95:5 to 90:10,from 90:10 to 80:20, from 80:20 to 70:30, from 70:30 to 60:40, from60:40 to 50:50, 50:50 to 40:60, from 40:60 to 30:70, from 30:70 to20:80, from 20:80 to 10:90, from 10:90 to 0:100, from 95:5 to 75:25,from 75:25 to 50:50, from 50:50 to 25:75, from 25:75 to 5:100, or anycombination of two or more of these ranges, including overlappingranges, for example from 90:10 to 75:25. In each case, the ratios aremole % cis/mol % trans. As described elsewhere,cis-N,N-dimethyl-3,5-lupetidinium cations, or mixtures containingpredominantly cis-N,N-dimethyl-3,5-lupetidinium cations are preferred.

As described above, the hydrothermal processes for preparing thecrystalline microporous aluminosilicate solid of GME topology requires,inter alia:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof and

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof.

In certain embodiments, the process is done in the absence of the sourceof aluminum oxide, boron oxide, gallium oxide, hafnium oxide, ironoxide, tin oxide, titanium oxide, indium oxide, vanadium oxide,zirconium oxide, or combination or mixture thereof.

In certain embodiments, the composition is absent any source of one ormore of boron oxide, gallium oxide, germanium oxide, hafnium oxide, ironoxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, orzirconium oxide.

In some embodiments, the sources of aluminum oxide, silicon oxide, oroptional source of boron oxide, gallium oxide, germanium oxide, hafniumoxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadiumoxide, zirconium oxide, or combination or mixture thereof comprises analkoxide, hydroxide, oxide, mixed metal oxide, or combination thereof.

The processes are described thus far in terms of “a source of a siliconoxide, and optionally a source of germanium oxide or combinationthereof” The use of a source of silicon oxide, germanium oxide, and anycombination thereof represent individual and independent embodiments.The presence of a source of silicon oxide, either by itself or incombination with sources of germanium oxide is preferred.

The source of silicon oxide may comprise an aluminosilicate, a silicate,silica hydrogel, amorphous silica, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicate, a silica hydroxide, silicon alkoxide,or combination thereof. Sodium silicate or tetraorthosilicates arepreferred sources. Corresponding sources of germanium oxide can includealkali metal orthogermanates, M₄GeO₄, containing discrete GeO₄ ⁴⁻ ions,GeO(OH)₃ ⁻, GeO₂(OH)₂ ²⁻, [(Ge(OH)₄)₈(OH)₃]³⁻ or neutral solutions ofgermanium dioxide contain Ge(OH)₄, or alkoxide or carboxylatederivatives thereof.

The source of aluminum oxide is or comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, an aluminum siloxide, analuminosilicate, or combination thereof. In some embodiments, amesoporous or zeolite aluminosilicate material may be used as a sourceof both aluminum oxide and silicon oxide. For example, FAU type zeolitesserve as useful precursors, for example in structures having Si/Al=2.6or higher

In the presence of appropriate starting materials, the resultingcrystalline compositions have the GME framework topology formed by theseprocesses. In some cases, these may be characterized as a zeolite CIT-9material.

Thus far, the processes (and associated compositions) have beendescribed as in terms of the use or presence of a mineralizing agentSuch a mineralizing agent typically comprises an aqueous hydroxidederived from an alkali metal or alkaline earth metal hydroxide, therebyrendering these compositions alkaline. In certain aspects of thisembodiment, the alkali metal or alkaline earth metal hydroxide, mayinclude, for example, LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂,Sr(OH)₂, or Ba(OH)₂. LiOH, NaOH, or KOH appear to be preferred. In somecases, the pH of the water is in a range of from 7 to 7.5, from 7.5 to8, from 8 to 8.5, from 8.5 to 9, from 9 to 9.5, from 9.5 to 10, from 10to 11, from 11 to 12, from 12 to 13, from 13 to 14, or higher, or anycombination of two or more of these ranges, for example, at least 11.Under these conditions, the oxide precursors can be expected to be atleast partially hydrated or hydrolyzed to their hydroxide forms.

The processes and compositions may also be defined in terms of theratios of the individual ingredients. In certain embodiments, the molarratio of Al:Si is in a range of 0.0067 to 0.5 (or the molar ratio ofSi:Al is in a range of from 2 to 150). In certain specific embodiments,the molar ratio of Al:Si is in a range of from 0.0067 to 0.008, from0.008 to 0.01, from 0.01 to 0.02, from 0.02 to 0.03, from 0.03 to 0.04,from 0.04 to 0.05, from 0.05 to 0.1, from 0.1 to 0.11, from 0.11 to0.12, from 0.12 to 0.13, from 0.13 to 0.14, from 0.14 to 0.15, from 0.15to 0.16, from 0.16 to 0.17, from 0.17 to 0.18, from 0.18 to 0.2, from0.2 to 0.22, from 0.22 to 0.24, from 0.24 to 0.26, from 0.26 to 0.28,from 0.28 to 0.3, from 0.3 to 0.32, from 0.32 to 0.34, from 0.34 to0.36, from 0.36 to 0.38, from 0.38 to 0.4, from 0.4 to 0.42, from 0.42to 0.44, from 0.44 to 0.46, from 0.46 to 0.48, from 0.48 to 0.5, or anycombination of two or more of these ranges, for example from 0.01 to0.5, or from 0.05 to 0.15. It should be appreciated that while thesestoichiometries are defined solely in terms of Si and Al, some portionor all of the Si content may be substituted by Ge, and some portion ofthe Al may be substituted by B, Ga, Hf, Fe, Sn, Ti, In, V, or Zr.

In certain embodiments, the molar ratio of the respective OSDA:Si is ina range of 0.01 to 0.75. In certain specific, the molar ratio of OSDA:Siis in a range of from 0.01 to 0.02, from 0.02 to 0.03, from 0.03 to0.04, from 0.04 to 0.05, from 0.05 to 0.1, from 0.1 to 0.11, from 0.11to 0.12, from 0.12 to 0.13, from 0.13 to 0.14, from 0.14 to 0.15, from0.15 to 0.16, from 0.16 to 0.17, from 0.17 to 0.18, from 0.18 to 0.2,from 0.2 to 0.22, from 0.22 to 0.24, from 0.24 to 0.26, from 0.26 to0.28, from 0.28 to 0.3, from 0.3 to 0.32, from 0.32 to 0.34, from 0.34to 0.36, from 0.36 to 0.38, from 0.38 to 0.4, from 0.4 to 0.42, from0.42 to 0.44, from 0.44 to 0.46, from 0.46 to 0.48, from 0.48 to 0.5,from 0.5 to 0.55, from 0.55 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7,from 0.7 to 0.75, or any combination of two or more of these ranges, forexample from 0.01 to 0.5, or from 0.1 to 0.5. Again, while described interms of Si alone, in additional embodiments, the reference to Si mayalso refer to the presence of Si, Ge, or both, such that the namedproportion of Si refers to the combined amounts of Si and Ge.

In other embodiments, the molar ratio of water:Si is in a range of 5 to50. In certain specific embodiments, the molar ratio of water:Si is in arange of from 5 to 6, from 6 to 7, from 7 to 8, from 8 to 9, from 9 to10, from 10 to 11, from 11 to 12, from 12 to 13, from 13 to 14, from 14to 15, from 15 to 16, from 16 to 17, from 17 to 18, from 18 to 19, from19 to 20, from 20 to 22, from 22 to 24, from 24 to 26, from 26 to 28,from 28 to 30, from 30 to 32, from 32 to 34, from 34 to 36, from 36 to38, from 38 to 40, from 40 to 42, from 42 to 44, from 44 to 46, from 46to 48, from 48 to 50, or any combination of two or more of these ranges,for example from 10 to 50 or from 10 to 25. Again, while these ratiosare described in terms of Si alone, in additional embodiments, theseratios may also refer to the presence of Si, Ge, or both, such that thenamed proportion of Si refers to the combined amounts of Si and Ge.

In other embodiments, the molar ratio of total hydroxide:Si is in arange of 0.1 to 1.25. As used herein, the term “total hydroxide”includes the amount of hydroxide introduced with the OSDA and separatelyadded, for example as the mineralizer or other sources. In certainspecific embodiments, the molar ratio of water:Si is in a range of from0.1 to 0.15, from 0.15 to 0.2, from 0.2 to 0.25, from 0.25 to 0.3, from0.3 to 0.35, from 0.35 to 0.4, from 0.4 to 0.45, from 0.45 to 0.5, from0.5 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7, from 0.7 to 0.75, from0.75 to 0.8, from 0.8 to 0.85, from 0.85 to 0.9, from 0.9 to 0.95, from0.95 to 1, from 1 to 1.05, from 1.05 to 1.1, from 1.1 to 1.15, from 1.15to 1.2, from 1.2 to 1.25, or any combination of two or more of theseranges, for example from 0.4 to 1. Again, while these ratios aredescribed in terms of Si alone, in additional embodiments, these ratiosmay also refer to the presence of Si, Ge, or both, such that the namedproportion of Si refers to the combined amounts of Si and Ge.

The hydrothermal treating is typically done at a temperature in a rangeof from about 100° C. to about 200° C. for a time effective forcrystallizing the respective crystalline microporous aluminosilicatesolid. Independent embodiments include those where the hydrothermaltreating is done at at least one temperature in a range of from about100° C. to 120° C., from 120° C. to 140° C., from 140° C. to 160° C.,from 160° C. to 180° C., from 180° C. to 200° C., or any combination oftwo or more of these ranges. In certain specific embodiments, thetemperature is in a range of from 120° C. to 180° C. These rangesprovide for convenient reaction times, though higher and lowertemperatures may also be employed. In some embodiment, thesetemperatures are applied for times in a range of from 1 hour to 14 days.In certain embodiments, the temperature is applied for time in a rangeof 1 to 6 hour, from 6 to 12 hours, from 12 to 24 hours, from 24 to 48hours, from 2 to 4 days, from 4 to 8 days, from 8 to 14 days, or anycombinations of two or more of these ranges, for example, from 12 to 48hours. Again, longer or shorter times may also be employed. Thishydrothermal treating is also typically done in a sealed autoclave, atautogenous pressures. Some exemplary reaction conditions are provided inthe Examples.

Once the initial aluminosilicate solids are prepared, the processesinclude embodiments further comprising isolating these solids. Thesecrystalline solids may be removed from the reaction mixtures by anysuitable means (e.g., filtration, centrifugation, etc.), washed, anddried. Such drying may be done in air at temperatures ranging from 25°C. to about 200° C. Typically, such drying is done at a temperature ofabout 100° C.

These crystalline microporous aluminosilicate solids may be furthermodified, for example, by incorporating metals with the pore structures,either before or after drying, for example by replacing some of thecations in the structures with additional metal cations using techniquesknown to be suitable for this purpose (e.g., ion exchange). Such cationscan include those of rare earth, Group 1, Group 2 and Group 8 metals,for example Li, Na, K, Ca, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pt, Pd, Re, Sn,Ti, V, W, Zn and their mixtures.

The isolated aluminosilicate products may be subject to furtherprocessing, such further comprising heating the isolated crystallinemicroporous solid at a temperature in a range of from about 250° C. toabout 550° C. to form an OSDA-depleted product. The heating is done inan oxidizing atmosphere, such as air or oxygen, or in the presence ofother oxidizing agents. In other embodiments, the heating is done in aninert atmosphere, such as argon or nitrogen.

In those embodiments where the processing involved heating, typicalheating rates include is 0.1° C. to 10° C. per minute and or 0.5° C. to5° C. per minute. Different heating rates may be employed depending onthe temperature range. Depending on the nature of the calciningatmosphere, the materials may be heated to the indicated temperaturesfor periods of time ranging from 1 to 60 hours or more, to produce acatalytically active product.

As used herein, the term “OSDA-depleted” (or composition having depletedOSDA) refers to a composition having a lesser content of OSDA after thetreatment than before. In preferred embodiments, substantially all(e.g., greater than 90, 95, 98, 99, or 99.5 wt %) or all of the OSDA isremoved by the treatment; in some embodiments, this can be confirmed bythe absence of a TGA endotherm associated with the removal of the OSDAwhen the product material is subject to TGA analysis or the absence orsubstantial absence of C or N in elemental analysis (prior to heating,composition is expected to comprise C, N, O, Si, Al, H, and optionallyLi, Na, K).

Further processing of these materials, whether modified or not, may alsocomprise contacting the isolated crystalline microporous aluminosilicatesolid with ozone or other oxidizing agent at a temperature in a range of100° C. to 200° C. for a time sufficient to form an OSDA-depletedaluminosilicate product. In certain of these embodiments, the heating isdone at a temperature of about 150° C. to form an OSDA-depleted product.The ozone-treatment can be carried out in a flow of ozone-containingoxygen (typically for 12 hours or more. but shorter could be feasible).Any oxidative environment treatment sufficient to remove the OSDA can beused. Such environments, for example, can involve the use of organicoxidizers (alkyl or aryl peroxides or peracids) or inorganic peroxides(e.g., H₂O₂).

Further processing of these materials, whether modified or not, may alsocomprise, heating the isolated crystalline microporous aluminosilicatesolid at a temperature in a range of from about 200° C. to about 600° C.in the presence of an alkali, alkaline earth, transition metal, rareearth metal, ammonium or alkylammonium salts (anions including halide,preferable chloride, nitrate, sulfate, phosphate, carboxylate, ormixtures thereof) to form a dehydrated or an OSDA-depleted product. Inother aspects, the heating is done in the absence of these added salts.In certain of these embodiments, the heating is done in the presence ofNaCl or KCl. In certain exemplary embodiments, the heating is done at atemperature in a range of from 500 to 600° C. In exemplary embodiments,the heating is done in either an oxidizing or inert atmosphere. Inexemplary embodiments, the heating is done at a slow heating rateinitially, e.g., from 0.1° C. to 10° C. per minute and/or from 0.5° C.to 5° C. per minute.

Such use of salts is consistent with the disclosures provided in USPatent Appl. Publ. No. 2002/0119887 to Q. Huo and N. A. Stephenson. Forwater removal, the aluminosilicate of GME topology is typically heatedto 350° C. For substantial OSDA removal, temperatures up to 500° C. aretypically employed. As described in Huo, the preferred salts includealkali metal (Li, Na, K, Rb, Cs) halides (preferably Cl); alkaline earth(Be, Mg, Ca, Sr, Be) nitrates or phosphates; aluminum, gallium, andindium carbonates; zinc sulfate; Ag, Cd borate or silicate; Ru, Rh, Pd,Pt, Au, or Hg carboxylates; La, Ce, Pr, Nd, Pm, or Sm sulfonates; Eu, Gdalkoxide; R_(4-n)N⁺H_(n) phenolates, where R is alkyl, n=0-4—asdescribed in Huo. In some cases, the excess salt or salts can beremoved, following calcination, by water (or other solvent) rinse or ina combination with ion-exchange and subsequent desolvation.

Once dehydrated or calcined, the dehydrated or OSDA-depleted crystallinemicroporous material may be treated with an aqueous ammonium or metalsalt or may be treated under conditions so as to incorporate at leastone type of alkaline earth metal or alkaline earth metal oxide or salt,or transition metal or transition metal oxide. In some embodiments, thesalt is a halide salt. Where the salt is an ammonium salt, the resultingaluminosilicate contains the ammonium cation which, after calcination,decomposes to provide the protonated aluminosilicate (in the hydrogenform). In other embodiments, the metal salt comprises one or more of K⁺,Li⁺, Na⁺, Rb⁺, Cs⁺:Co²⁺, Ca²⁺, Mg²⁺, Sr²⁺; Ba²⁺; Ni²⁺; or Fe²⁺. In otherspecific embodiments, the metal cation salt is a copper salt, forexample, Schweizer's reagent (tetraaminediaquacopper dihydroxide,[Cu(NH₃)₄(H₂O)₂](OH)₂]), copper(II) nitrate, copper (II) diacetate (orother dicarboxylate), or copper(II) carbonate.

The addition of a transition metal or transition metal oxide may beaccomplished, for example by chemical vapor deposition or chemicalprecipitation. As used herein, the term “transition metal” refers to anyelement in the d-block of the periodic table, which includes groups 3 to12 on the periodic table. In actual practice, the f-block lanthanide andactinide series are also considered transition metals and are called“inner transition metals. This definition of transition metals alsoencompasses Group 4 to Group 12 elements. In certain independentembodiments, the transition metal or transition metal oxide comprises anelement of Groups 6, 7, 8, 9, 10, 11, or 12. In other independentembodiments, the transition metal or transition metal oxide comprisesscandium, yttrium, titanium, tin, zirconium, vanadium, manganese,chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt,rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, ormixtures. Fe, Ru, OS, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixturesthereof are preferred.

Intermediate Reaction Compositions

As described herein, the as-formed and post-treated crystallinealuminosilicate compositions themselves are within the scope of thepresent disclosure and are considered to be independent embodiments ofthe present invention. All of the descriptions used to describe thefeatures of the inventive processes are also considered to apply tothese compositions. In an abundance of caution, some of these arepresented here, but these descriptions should not be considered toexclude embodiments provided elsewhere.

Included in these embodiments are compositions comprising the aqueouscompositions used in the hydrothermal treatments together with therespective crystalline microporous aluminosilicate products, wherein thealuminosilicate products contain the respective OSDAs used in theirpreparation occluded in their pores.

For example, in some embodiments, the composition comprises:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide, or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a mineralizing agent;

(d) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I) (or any ofthe embodied cations of Formula (I) described elsewhere in thisdisclosure);

and

(e) a compositionally consistent crystalline microporous aluminosilicatesolid of GME topology.

As used herein, the term “compositionally consistent” refers to acrystalline aluminosilicate composition having a stoichiometry resultingfrom the crystallization of the of sources of oxides in the presence ofpiperidinium OSDAs; i.e., the OSDAs of Formula (I). In some of theseembodiments, for example, this term reflects a composition which is theresult of at least a partial progression of the hydrothermal treatingprocess used to prepare these materials. Typically, thesecompositionally consistent crystalline microporous aluminosilicatesolids contain, occluded in their pores, the OSDA used to make them;i.e., the OSDA present in the associated aqueous composition, and suchis within the scope of the present disclosure.

In separate embodiments, these compositionally consistent crystallinemicroporous aluminosilicate solids may be substantially free of theOSDAs used in the aqueous media; in such embodiments, thealuminosilicate may be used as seed material for the crystallization.

These compositions may comprise any of the types and ratios ofingredients and may exist at temperatures consistent with the processingconditions described above as useful for the hydrothermal processing. Itshould be appreciated that this disclosure captures each and every ofthese permutations as separate embodiments, as if they were separatelylisted. In some embodiments, these compositions exist in the form of agel or suspension.

Crystalline Microporous Compositions

In addition to the processing and process compositions, themicrocrystalline products are also considered within the scope of thepresent invention. In particular, any product prepared by theseinventive methods is considered an embodiment of this invention. Again,in preferred embodiments, the crystalline microporous aluminosilicatesolid is preferably one of entirely GME topology. But separateembodiments also provide that the crystalline microporous solid may alsocontain other structural phases or phase mixtures, next to the GMEphase.

These isolated microporous aluminosilicate solid of GME topology maycontain any of the piperidinium OSDAs described herein occluded in theirpores—i.e., the OSDAs of Formula (I) within the framework—or they may bedevoid or substantially devoid of such organic materials (the terms“devoid” and “substantially devoid” being quantitatively analogous tothe term “OSDA depleted”).

The presence of the OSDAs may be identified using, for example ¹³C NMR,elemental analysis for C and N, or any of the methods defined in theExamples. It is a particular feature of the present invention that thecationic OSDAs retain their original structures, including theirstereochemical conformations during the synthetic processes, thesestructures being compromised during the subsequent calcinations.

More specifically, some embodiments provide crystalline microporousaluminosilicate solids having pores at least some of which are occludedwith quaternary piperidinium cations of Formula (I), in any of theembodiments described herein for these cations. In other embodiments,the pores are substantially OSDA-depleted.

Such aluminosilicate solids may also be described in terms of theirSi:Al molar ratios, as well as their physical characteristics. Incertain embodiments, the crystalline microporous aluminosilicate solidare characterized as having a molar ratio of Si:Al in a range of from2.5 to about 100 (or SiO₂/Al₂O₃ ratio greater than 7 to about 30).Independent aspects of this embodiment include those where the Si/Alratio is in a range of from 2.5 to 2.6, from 2.6 to 2.7, from 2.7 to2.8, from 2.8 to 2.9, from 2.9 to 3, from 3 to 3.2, from 3.2 to 3.4,from 3.4 to 3.6, from 3.6 to 3.8, from 3.8 to 4, from 4 to 4.2, from 4.2to 4.4, from 4.4 to 4.6, from 4.6 to 4.8, from 4.8 to 5, from 5 to 5.2,from 5.2 to 5.4, from 5.4 to 5.6, from 5.6 to 5.8, from 5.8 to 6 from 6to 6.4, from 6.4 to 6.8, from 6.8 to 7.2, from 7.2 to 7.6, from 7.6 to8, from 8 to 8.4, from 8.4 to 8.8, from 8.8 to 9.2, from 9.2 to 9.6 from9.6 to 10, from 10 to 10.4, from 10.4 to 10.8, from 10.8 to 11.2, from11.2 to 11.6, from 11.6 to 12, from 12 to 12.4, from 12.4 to 12.8, from12.8 to 13.2, from 13.2 to 13.6, from 13.6 to 14.0, from 14 to 14.5,from 14.5 to 15, from 15 to 20, from 20 to 25, from 25 to 30, from 30 to35, from 35 to 40, from 40 to 50, from 50 to 60, from 60 to 70, from 70to 80, from 80 to 90, from 90 to 100, or any combination of two or moreof these range, for example from 2.5 to 30, from greater than 3.5 (e.g.,3.6) to 100, or from greater than 3.5 to 30. In some embodiments wherethe aluminosilicate compositions contain occluded quaternarypiperidinium OSDAs, the molar ratio of Si:Al is in any range or subrangeof from 2.5 to about 100 described above. In other embodiments, wherethe aluminosilicate compositions contains no, or substantially no (e.g.,substantially free of) quaternary piperidinium cation OSDA, the molarratio of Si:Al is in any range or subrange of from greater than 3.5 to100 described above.

The crystalline microporous aluminosilicate solids may alsocharacterized by their physical properties. In specific embodiments, thecrystalline microporous solid exhibits one or more of thecharacteristics associated with CIT-9. In other embodiments, thesealuminosilicate solid exhibit at least one of the followingcharacteristics:

(a) an XRD pattern having at least the five major peaks substantially asprovided in Table 2.

(b) an XRD diffraction pattern the same as or consistent with any one ofthose shown in FIG. 3 , FIG. 6 , FIG. 7 , or FIG. 13 ;

(c) an ²⁹Si MAS spectrum having a plurality of chemical shifts of about−99.1, −104.9 and −110.5 ppm downfield of a peak corresponding to andexternal standard of tetramethylsilane;

(d) an ²⁹Si MAS spectrum the same as or consistent with the one shown inFIG. 12 ;

(f) an physisorption isotherm with N₂-gas or with argon the same as orconsistent with any one of those shown in FIG. 10 ; or

(e) an ²⁷Al MAS NMR spectrum the same as or consistent with the oneshown in FIG. 11 .

Additional embodiments include those compositions which exhibit (f) athermogravimetric analysis curve the same as or consistent with the oneshown in FIG. 4 ; the TGA indicative of a loss of 8 to 16 wt %, possiblydue to the removal of the OSDA; (g) a ¹³C CP MAS NMR spectra the same asor consistent with the one shown in FIG. 5 .

The disclosed crystalline microporous aluminosilicate compositionsinclude those which result from the post-treatment or further processingdescribed in the processing section. These include thosealuminosilicates which are in their hydrogen forms or have cations,metals or metal oxides within their pore structures. Accordingly, incertain embodiments, the microporous aluminosilicate solids have GMEtopologies, containing Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga,In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, orR_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4 in at least some oftheir pores. In specific aspects of these embodiments, these porescontain NaCl or KCl.

Additional embodiments include those crystalline microporousaluminosilicate solids having GME topology, at least some of whose porestransition metals, transition metal oxides, or salts, for examplescandium, yttrium, tin, titanium, zirconium, vanadium, manganese,chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt,rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, ormixtures thereof, each as a metal, oxide, or salt. In one specificembodiment, the pores of the aluminosilicate solids contain copper, asmetal, oxide, or salt.

Use of the Inventive Compositions

The calcined crystalline microporous solids, calcined or doped ortreated with the catalysts described herein may also be used ascatalysts for a variety of chemical reactions, including carbonylatingDME with CO at low temperatures, reducing NOx with methane, reducing NOxwith ammonia, cracking, dehydrogenating, converting paraffins toaromatics, MTO (methanol-to-olefin), isomerizing xylenes,disproportionating toluene, alkylating aromatic hydrocarbons,oligomerizing alkenes, aminating lower alcohols, separating and sorbinglower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbonfeedstock, isomerizing an olefin, producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon, reforming ahydrocarbon, converting a lower alcohol or other oxygenated hydrocarbonto produce an olefin products, reducing the content of an oxide ofnitrogen contained in a gas stream in the presence of oxygen, orseparating nitrogen from a nitrogen-containing gas mixture by contactingthe respective feedstock with a catalyst comprising one or more of thecrystalline microporous aluminosilicate solids described herein underconditions sufficient to affect the named transformation. Thesecatalysts appear to be especially suitable for converting paraffins intoaromatics (e.g., hexane to benzene) and for carbonylating DME with CO atlow temperatures.

The GME framework topology is also interesting for applications insorption. Sorption applications could potentially be found inhydrocarbon separation processes and ion-exchange. Catalytic processesof interest include, but are not limited to, the aromatization ofnaphtha, the dehydrocyclization of hexane, hydrocarbon isomerizationand/or chlorination.

Specific conditions for many of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961 and U.S.Pat. No. 4,544,538, both of which are incorporated by reference hereinin its entirety for all purposes.

Depending upon the type of reaction that is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. As used herein, “predominantly in thehydrogen form” means that, after calcination (which may also includeexchange of the pre-calcined material with NH₄ ⁺ prior to calcination),at least 80% of the cation sites are occupied by hydrogen ions and/orrare earth ions.

The following listing of embodiments is intended to complement, ratherthan displace or supersede, any of the previous descriptions.

Embodiment 1. A process for preparing an aluminosilicate compositionhaving a GME topology, the process comprising hydrothermally treating anaqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a mineralizing agent; and

(d) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporousaluminosilicate solid of GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiments, the crystalline microporousaluminosilicate solid of GME topology has a molar ratio of Si:Al greaterthan 3.5.

In some Aspects of this Embodiment, the OSDA comprises at least oneisomer of the quaternary piperidinium cation of Formula (IA) or (IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.

Embodiment 2. The process of Embodiment 1, wherein the quaternarypiperidinium cation of Formula (I) is or comprises anN,N-dialkyl-2,6-lupetidinium cation or an N,N-dialkyl-3,5-lupetidiniumcation:

In separate Aspects of this Embodiment, the quaternary piperidiniumcation of Formula (I) is an N,N-dialkyl-2,6-lupetidinium cation. Inother Aspects, it is an N,N-dialkyl-3,5-lupetidinium cation.

Embodiment 3. The process of Embodiment 1 or 2, wherein the quaternarypiperidinium cation of Formula (I) is or comprisescis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 4. The process of Embodiment 2 or 3, wherein R^(A)′ and R^(B)are both methyl.

Embodiment 5. The process of any one of Embodiments 1 to 4, wherein thequaternary piperidinium cation has an associated fluoride or hydroxideion preferably substantially free of other halide counterions. Inseparate Aspects of this Embodiment, the associated anion is hydroxide.

Embodiment 6. The process of any one of Embodiments 1 to 5, wherein thecomposition being hydrothermally treated is or comprises a source ofsilicon oxide and a source of aluminum oxide. In other Aspects of thisEmbodiment, some of the sources of silicon oxide and aluminum oxidederive from common sources, for example, an aluminosilicate. In otherAspects of this Embodiment, the composition is absent any source of oneor more of boron oxide, gallium oxide, germanium oxide, hafnium oxide,iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, orzirconium oxide.

Embodiment 7. The process of any one of Embodiments 1 to 6, wherein thesource of aluminum oxide, silicon oxide, or optional source of boronoxide, gallium oxide, germanium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination or mixture thereof comprises an alkoxide, hydroxide, oxide,mixed metal oxide, or combination thereof.

Embodiment 8. The process of any one of Embodiments 1 to 7, wherein thesource of silicon oxide is or comprises an aluminosilicate, a silicate,silica hydrogel, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicate, a silica hydroxide or combination thereof. Itshould be appreciated that in certain Aspects of this Embodiment, thealuminosilicate or silicate is of a topology or composition differentthan the topology or composition of the intended product (e.g.,different than the GME topology eventually prepared and/or isolated). Inother Aspects of this Embodiment, the aluminosilicate or silicate is thesame topology or composition as the topology or composition of theintended product, for example, acting as seeds.

Embodiment 9. The process of any one of Embodiments 1 to 8, wherein thesource of aluminum oxide is or comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, an aluminum siloxide, analuminosilicate, or combination thereof. It should be appreciated thatin certain Aspects of this Embodiment, the aluminosilicate is of atopology or composition different than the topology or composition ofthe intended product (e.g., different than the GME topology eventuallyprepared and/or isolated). In other Aspects of this Embodiment, thealuminosilicate is the same topology or composition as the topology orcomposition of the intended product, for example, acting as seeds

Embodiment 10. The process of any one of Embodiments 1 to 9, wherein thesource of silicon oxide is or comprises sodium silicate, for examplefrom a FAU-zeolite. In certain Aspects of this Embodiment, theFAU-zeolite may also provide at least a part of the source of aluminumoxide.

Embodiment 11. The process of any one of Embodiments 1 to 10, whereinthe mineralizing agent is or comprises an aqueous hydroxide. In certainAspects of this Embodiment, the hydroxide is an alkali metal or alkalineearth metal hydroxide, for example including LiOH, NaOH, KOH, RbOH,CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂.

Embodiment 12. The process of any one of Embodiments 1 to 11, whereinthe molar ratio of Al:Si is in a range of from 0.0067 to 0.5 (or themolar ratio of Si:Al is in a range of from 2 to 150). In certainspecific Aspects of this Embodiment, the molar ratio of Al:Si is in arange of from 0.01 to 0.5, or from 0.05 to 0.15.

Embodiment 13. The process of any one of Embodiments 1 to 12, whereinthe molar ratio of OSDA:Si is in a range of from 0.01 to 0.75. Incertain specific Aspects of this Embodiment, the molar ratio of OSDA:Siis in a range of from 0.01 to 0.5, or from 0.1 to 0.5.

Embodiment 14. The process of any one of Embodiments 1 to 13, whereinthe molar ratio of water:Si is in a range of from 5 to 50. In certainspecific Aspects of this Embodiment, the molar ratio of water:Si is in arange of from 10 to 50 or from 10 to 25.

Embodiment 15. The process of any one of Embodiments 1 to 14, whereinthe molar ratio of total hydroxide:Si is in a range of 0.1 to 1.25. Incertain specific Aspects of this Embodiment, the molar ratio of totalhydroxide:Si is in a range of from 0.5 to 1.

Embodiment 16. The process of any one of Embodiments 1 to 15, whereinthe conditions effective to crystallize a crystalline microporous solidof GME topology include treatment of the hydrothermally treatedcomposition at a temperature in a range of from 100° C. to 200° C. Incertain specific Aspects of this Embodiment, the temperature is in arange of from 120° C. to 180° C. In certain independent Aspects of thisEmbodiment, the times and temperatures include ranges describedelsewhere herein.

Embodiment 17. The process of any one of Embodiments 1 to 14, whereinthe hydrothermally treating is done at a temperature in a range of fromabout 100° C. to about 200° C. for a time effective for crystallizingthe crystalline microporous solid of GME topology. In certain specificAspects of this Embodiment, this time is in a range of from 1 hour to 14days. In certain independent Aspects of this Embodiment, the times andtemperatures include ranges described elsewhere herein.

Embodiment 18. The process of any one of Embodiments 1 to 17, furthercomprising isolating the crystalline microporous aluminosilicate solidof GME topology.

Embodiment 19. The process of Embodiment 18, further comprising heatingthe isolated crystalline microporous solid at a temperature in a rangeof from about 250° C. to about 450° C. to form an OSDA-depleted product.In certain independent Aspects of this Embodiment, the heating is donein an oxidizing atmosphere, such as air or oxygen, or in the presence ofother oxidizing agents. In other Aspects, the heating is done in aninert atmosphere, such as argon or nitrogen.

Embodiment 20. The process of Embodiment 18, further comprisingcontacting the isolated crystalline microporous solid with ozone orother oxidizing agent at a temperature in a range of 100° C. to 200° C.for a time sufficient to form an OSDA-depleted crystalline microporoussolid. In certain specific Aspects of this Embodiment, the heating isdone at a temperature of about 150° C. to form an OSDA-depleted product.In other Aspects of this Embodiment, the heating is done for a timesufficient to substantially remove any occluded OSDA from the pores ofthe zeolite.

Embodiment 21. The process of Embodiment 18, further comprising heatingthe isolated crystalline microporous solid at a temperature in a rangeof from about 200° C. to about 600° C. in the absence or presence of analkali, alkaline earth, transition metal, rare earth metal, ammonium oralkylammonium salts (anions including halide, preferable chloride,nitrate, sulfate, phosphate, carboxylate, or mixtures thereof) to form adehydrated or an OSDA-depleted product. In certain Aspects of thisEmbodiment, the heating is done in the presence of NaCl or KCl. Aspectsof this Embodiment, the heating is done at a temperature in a range offrom 500 to 600° C. In still other Aspects of the Embodiment, theheating is done in either an oxidizing or inert atmosphere.

Embodiment 22. The process of any one of Embodiments 19 to 21, furthercomprising treating the dehydrated or OSDA-depleted product with anaqueous alkali, alkaline earth, transition metal, rare earth metal,ammonium or alkylammonium salts, preferably a halide salt. In someAspects of this Embodiment, the salt is a halide salt. In some Aspectsof this Embodiment, the metal salt comprises K⁺, Li⁺, Rb⁺, Cs⁺:Co²⁺,Ca²⁺, Mg²⁺, Sr²⁺; Ba²⁺; Ni²⁺; Fe²⁺. In other specific Aspects, the metalcation salt is a copper salt, for example, Schweizer's reagent(tetraamminediaquacopper dihydroxide, [Cu(NH₃)₄(H₂O)₂](OH)₂]),copper(II) nitrate, or copper(II) carbonate.

Embodiment 23. The process of any one of Embodiments 19 to 22, furthercomprising treating at least some pores of the calcined crystallinemicroporous solid with at least one type of transition metal ortransition metal oxide. In certain Aspects of this Embodiment, thetransition metal or transition metal oxide comprises a Group 4 to Group12 metal. In certain independent Aspects of this Embodiment, thetransition metal or transition metal oxide comprises an element ofGroups 6, 7, 8, 9, 10, 11, or 12. In other independent Aspects of thisEmbodiment, the transition metal or transition metal oxide comprises Fe,Ru, OS, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.

Embodiment 24. A composition prepared by any one of the processes ofEmbodiments 1 to 23. In certain Aspects of this Embodiment, thecomposition comprises an aluminosilicate having a molar ratio of Si:Alis in a range of from about 2.5 to 100. Independent Aspects of thisEmbodiment include those described elsewhere herein in this context.

Embodiment 25. A composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide, or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof;

(c) a mineralizing agent (preferably hydroxide);

(d) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

and

(e) a compositionally consistent crystalline microporous aluminosilicatesolid of GME topology;

wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiments, the crystalline microporousaluminosilicate solid of GME topology has a molar ratio of Si:Al in arange of from 2.5 to 100, or any of the subranges described in thiscontext, elsewhere herein.

In other Aspects of this Embodiment, the OSDA comprises at least oneisomer of the quaternary piperidinium cation of Formula (I):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion. Eachof these cations is an independent Aspect of this Embodiment. In certainAspects of this Embodiment, the composition is one characterized as aCIT-9 composition as described herein. In other Aspects of thisEmbodiment, the composition is absent any source of aluminum oxide,boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, or zirconium oxide.

Embodiment 26. The composition of Embodiment 25, wherein the quaternarypiperidinium cation of Formula (I) is an N,N-dialkyl-2,6-lupetidiniumcation or N,N-dialkyl-3,5-lupetidinium cation:

Embodiment 27. The composition of Embodiment 25, wherein the quaternarypiperidinium cation of Formula (I) is cis-N,N-dialkyl-3,5-lupetidiniumcation, trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof or amixture of OSDAs containing these cations:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 28. The composition of Embodiment 26 or 27, wherein R^(A)′and R^(B) are both methyl.

Embodiment 29. The composition of any one of Embodiments 25 to 28,containing a source of silicon oxide and a source of aluminum. Incertain Aspects of this Embodiment, the optionally sources of germaniumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, or zirconium oxide areabsent.

Embodiment 30. The composition of any one of Embodiments 25 to 29,wherein the source of silicon oxide is or comprises an aluminosilicate,a silicate, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicate, a silica hydroxide or combinationthereof.

Embodiment 31. The composition of any one of Embodiments 25 to 30,wherein the source of aluminum oxide is or comprises an alkoxide,hydroxide, or oxide of aluminum, a sodium aluminate, an aluminumsiloxide, an aluminosilicate, or combination thereof.

Embodiment 32. The composition of any one of Embodiments 25 to 31,wherein the source of silicon oxide is or comprises sodium silicate andthe source of Al is or comprises a FAU-zeolite

Embodiment 33. The composition of any one of Embodiments 25 to 32,wherein the mineralizing agent comprises aqueous hydroxide. In certainAspects of this Embodiment, the hydroxides is an alkali metal oralkaline earth metal hydroxide, including LiOH, NaOH, KOH, RbOH, CsOH,Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂.

Embodiment 34. The composition of any one of Embodiments 25 to 33,wherein the molar ratio of Al:Si in the composition is in a range of0.0067 to 0.5 (or the molar ratio of Si:Al is in a range of from 2 to150). In certain specific Aspects of this Embodiment, the molar ratio ofAl:Si is in a range of from 0.01 to 0.5, or from 0.05 to 0.15.

Embodiment 35. The composition of any one of Embodiments 25 to 34,wherein the molar ratio of OSDA:Si in the composition is in a range offrom 0.01 to 0.75. In certain specific Aspects of this Embodiment, themolar ratio of OSDA:Si is in a range of from 0.01 to 0.5, or from 0.1 to0.5

Embodiment 36. The composition of any one of Embodiments 25 to 35,wherein the molar ratio of water:Si in the composition is in a range offrom 5 to 75. In certain specific Aspects of this Embodiment, the molarratio of water:Si is in a range of from 10 to 50 or from 10 to 25.

Embodiment 37. The composition of any one of Embodiments 25 to 36,wherein the molar ratio of total hydroxide:Si in the composition is in arange of 0.1 to 1.25. In certain specific Aspects of this Embodiment,the molar ratio of total hydroxide:Si is in a range of from 0.5 to 1.

Embodiment 38. The composition of any one of Embodiments 25 to 37 thatis a suspension or gel.

Embodiment 39. A crystalline microporous aluminosilicate solid of GMEtopology having pores at least some of which are occluded with at leastone isomer of the quaternary piperidinium cation of Formula (I):

wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiments, the crystalline microporousaluminosilicate solid of GME topology has a molar ratio of Si:Al greaterthan 3.5.

In other Aspects of this Embodiment, the OSDA is or comprises at leastone isomer of the quaternary piperidinium cation of Formula (IA) or(IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion. Incertain Aspects of this Embodiment, the composition is one characterizedas a CIT-9 composition as described herein.

Embodiment 39. The crystalline microporous solid of Embodiment 35 or 36,wherein the quaternary piperidinium cation of Formula (I) or (II) is anN,N-dialkyl-2,6-lupetidinium cation or N,N-dialkyl-3,5-lupetidiniumcation:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 40. The crystalline microporous solid of any one ofEmbodiments 35 to 37, wherein the quaternary piperidinium cation ofwherein the quaternary piperidinium cation of Formula (I) or (II) iscis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof or amixture of OSDAs containing such a cation:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 41. The crystalline microporous solid of any one ofEmbodiments 39 to 41, wherein R^(A)′ and R^(B) are both methyl.

In certain Aspects, the crystalline microporous aluminosilicate of anyone of Embodiments 39 to 41 has a Si/Al molar ratio in a range of from2.5 to about 100 (or SiO₂/Al₂O₃ ratio greater than 5 to about 200).Independent Aspects of this Embodiment include those described elsewhereherein in this context. In specific Aspects of this Embodiment, thecrystalline microporous solid exhibits one or more of thecharacteristics associated with CIT-9.

Embodiment 42. A crystalline microporous solid comprising (a) siliconoxide, and optionally germanium oxide, or combination thereof and (b)aluminum oxide, and optionally boron oxide, gallium oxide, hafniumoxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadiumoxide, zirconium oxide, or combination thereof, and having a GMEtopology and the solid exhibiting at least one of the following:

(a) an XRD pattern having at least the five major peaks substantially asprovided in Table 2.

(b) an XRD diffraction pattern the same as or consistent with any one ofthose shown in FIG. 3 , FIG. 6 , FIG. 7 , or FIG. 13 ;

(c) an ²⁹Si MAS spectrum having a plurality of chemical shifts of about−99.1, −104.9 and −110.5 ppm downfield of a peak corresponding to andexternal standard of tetramethylsilane;

(d) an ²⁹Si MAS spectrum the same as or consistent with the one shown inFIG. 12 ;

(f) an physisorption isotherm with N₂-gas or with argon the same as orconsistent with any one of those shown in FIG. 10 ;

(e) an ²⁷Al MAS NMR spectrum the same as or consistent with the oneshown in FIG. 11 ;

(f) a molar ratio of Si:Al that is greater than 3.5 to about 100 (orSiO₂/Al₂O₃ ratio greater than 7 to about 200); or

(g) a molar ratio of Si:Al that is greater than 2.5 to about 100 (orSiO₂/Al₂O₃ ratio greater than 7 to about 200), wherein the crystallinemicroporous solid contains at least one quaternary piperidinium cationof Formula (I).

Additional Aspects of this Embodiment embodiments include thosecompositions which exhibit (f) a thermogravimetric analysis curve thesame as or consistent with the one shown in FIG. 4 ; the TGA indicativeof a loss of 8 to 16 wt %, possibly due to the removal of the OSDA; (g)a ¹³C CP MAS NMR spectra the same as or consistent with the one shown inFIG. 5 . In specific Aspects of this Embodiment, the crystallinemicroporous solid exhibits one or more of the characteristics associatedwith CIT-9.

Embodiment 43. A crystalline microporous aluminosilicate of GME topologyhaving a Si/Al molar ratio in a range of from greater than 3.5 to about100 (or SiO₂/Al₂O₃ ratio greater than 7 to about 200). IndependentAspects of this Embodiment include those where the molar Si/Al ratio isdescribed elsewhere herein. In certain Aspects of this Embodiment, thecrystalline microporous aluminosilicate contains one or more of thequaternary piperidinium-containing OSDA described herein occluded withinits pores. In other Aspects, the crystalline microporous aluminosilicateis devoid or substantially devoid of such piperidinium-containing OSDAs.Aspects of this Embodiment, the crystalline microporous solid exhibitsone or more of the characteristics associated with CIT-9.

Embodiment 44. The crystalline microporous solid of Embodiment 42 or 43,comprising pores, at least some of which contain Li, Na, K, Rb, Cs, Be,Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce,Pr, Nd, Pm, Sm, Eu, or R_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4.In specific Aspects of this Embodiment, the pores contain NaCl or KCl.

Embodiment 45. The crystalline microporous solid of any one ofEmbodiments 42 to 44, comprising pores, at least some of which containscandium, yttrium, titanium, tin, zirconium, vanadium, manganese,chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt,rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, ormixtures thereof, each as a metal, oxide, or salt. In one Aspect of thisEmbodiment, the pores contain copper, as metal, oxide, or salt.

Embodiment 46. A process comprising carbonylating DME with CO at lowtemperatures, reducing NOx with methane, cracking, dehydrogenating,converting paraffins to aromatics, MTO, isomerizing xylenes,disproportionating toluene, alkylating aromatic hydrocarbons,oligomerizing alkenes, aminating lower alcohols, separating and sorbinglower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbonfeedstock, isomerizing an olefin, producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon, reforming ahydrocarbon, converting a lower alcohol or other oxygenated hydrocarbonto produce an olefin products, reducing the content of an oxide ofnitrogen contained in a gas stream in the presence of oxygen, orseparating nitrogen from a nitrogen-containing gas mixture by contactingthe respective feedstock with a catalyst comprising the crystallinemicroporous solid of any one of Embodiments 42 to 45 under conditionssufficient to affect the named transformation. In specific Aspects ofthis Embodiments, the process comprises converting paraffins intoaromatics (hexane to benzene) and carbonylating DME with CO at lowtemperatures

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees Celsius, pressure is ator near atmospheric, or autogenous for the solution at that temperature.

Example 1. General Methods Example 1.1. Materials and Methods

N,N-dimethyl-3,5-lupetidinium hydroxide was acquired from SACHEM Inc.

All PXRD characterization was conducted on a Rigaku MiniFlex II with CuK_(α) radiation.

¹³C CP MAS solid state NMR MAS spectra were recorded on a Bruker 500 MHzspectrometer in a 4 mm ZrO₂ rotor spinning at 8 kHz and referenced toadamantane as external standard. Solid-state ²⁷Al MAS NMR was acquiredon a Bruker AM 300 MHz spectrometer operated at 78.2 MHz using a 90°pulse length of 2 μs and a cycle delay time of 1 s. Samples were loadedin a 4 mm ZrO₂ rotor and spun at 12 kHz. Chemical shifts were referencedto 1 M aqueous aluminum nitrate solution. ²⁹Si NMR was measured on aBruker 500 MHz spectrometer in a 4 mm ZrO₂ rotor at a spinning rate of 8kHz and referenced externally versus tetramethylsilane.

Thermogravimetric analysis (TGA) was performed on a Perkin Elmer STA6000 with a ramp of 10° C.min⁻¹ to 900° C. under air atmosphere.

SEM was performed on a ZEISS 1550 VP FESEM, equipped with an OxfordX-Max SDD X-ray Energy Dispersive Spectrometer (EDS) system fordetermining the Si/Al ratios of the samples.

The N₂ and Ar adsorption isotherms were performed at −196° C. and −186°C. respectively, with a Quantachrome Autosorb iQ instrument. Prior toanalysis, the samples were outgassed under vacuum at 200° C. The t-plotmethod was used to calculate the micropore volumes on the adsorptionbranch.

Example 1.2. General Synthetic Methods

Syntheses in Table 1 were performed with this OSDA in its hydroxideform. A general procedure for hydroxide syntheses was as follows. TheOSDA in its hydroxide form was combined with additional base (1M sodiumhydroxide, RT Baker) and water in a 23 mL-Teflon Parr reactor. Then asilica source was added (N^(o) Sodium silicate (PQ Corporation) as wellas an aluminum source (CBV500=NH₄-FAU of Zeolyst). The synthesis wasstirred until a homogenous gel was obtained. The Teflon Parr reactor wasthen sealed and placed in a rotating or static oven at 140° C. Aliquotsof the synthesis gels were taken periodically as follows: quenching thereactor in water, opening the reactor, stirring its contents tillhomogeneous and finally, removing enough material for PXRD. Afterwashing the aliquots once with water and once with acetone, they areleft to dry in a 100° C. oven before PXRD measurement. The yields werecalculated as follows: the final dry weight obtained after thoroughwashing of the finished syntheses with water and acetone and drying at100° C. is corrected with the weight loss of organic OSDA and water inTGA up to 900° C. This corrected weight is assumed to be purealuminosilicate and is divided by the maximum theoretical possiblealuminosilicate formation from the input silica and alumina. The weightof sodium cation present in the samples is hereby neglected.

The ozonolysis procedure for SDA removal was carried out at 150° C. in atube furnace by using a Longevity Resources ozone generator (setting at2) and an oxygen gas flow of 200 cm³/min over 100-500 mg of as-madezeolite sample. Ion-exchanges were performed in 1M nitrate saltsolutions at 80° C. for 2 h under stirring with 1 g zeolite per 100 mLand this was repeated 3 times.

The calcination of K⁺-CIT-9 was performed in dry flowing air by heatingto 150° C. at 1° C./min; holding for 3 h at 150° C., and then heatedfurther to 580° C. at 1° C./min and held for 6 h.

Example 2. Syntheses and Characterizations

Table 1 shows typical CIT-9 (GME) syntheses. It was found that pure GMEcould be made, free of powder X-ray diffraction (PXRD)-visible CHAimpurities (usually seen at 20 values of 9.4; 15.9 and 20.4), using thequaternized N,N-dimethyl-3,5-dimethylpiperidine structure directingagent. This OSDA is structurally illustrated in FIG. 2 .

TABLE 1 Typical CIT-9 (GME) syntheses reactions withN,N-dimethyl-3,5-dimethylpiperidine hydroxide (98 cis/2% trans) as theOSDA, NH₄-FAU (CBV500, Si/Al 2.6) as aluminum source and sodium silicateas silicon source. Gel composition relative to Si¹ (i.e., molar ratiosbased on Si = 1) Time TGA² Yield Sample Entry Al OSDA H₂O OH⁻ NaOH (h)phase Si/Al (wt %) (%) name 1 0.067 0.17 20.7 0.71 0.54 54 GME 4.0 14.1%24% MDU80  2³ 0.067 0.17 19.9 0.71 0.54 48 GME 4.0 13.7% 35% MDU93 30.066 0.17 20.5 0.70 0.53 63 GME⁴ 5.0 12.3%  33%⁵ MDU53 4 0.022 0.1720.1 0.76 0.59 54 GME 4.8 — <10%⁶   MDU22 5 0.033 0.17 20.0 0.74 0.57 54GME⁷ — — — MDU19 6 0.033 0.14 11.9 0.71 0.57 48 GME 4.1 15.6% 13% MDU190 7⁸ 0.33 0.375 22.1 0.875 0.5 48 GME⁹ n.d. n.d. n.d. — ¹NaOH:Si iscalculated from the total Na content, originating from NaOH addition andsodium silicate. Synthesis in rotating oven at 140° C. OH⁻ is the sum ofinorganic and OSDA derived hydroxide contents. ²Weight % loss in TGAbetween 300° C. and 900° C. relative to the amount of zeolite left at900° C. ³Syntheses in a static oven at 140° C. ⁴ANA impurity (densephase). ⁵Yield after 115 h, but both PXRD at 63 h and 115 h were absentof starting FAU. After 63 h, the ANA impurity reflections became moreintense, ⁶Yield after 7 days, but PXRD after 54 h and 7 days wereidentical and absent of starting FAU. ⁷AEI impurity. ⁸Using 50/50cis-trans N,N-dimethyl-3,5-dimethylpiperidine hydroxide. ⁹ANA impurity.

Table 1 shows a range of successful GME syntheses conditions.Furthermore, it is seen in these examples that the molar Si/Al ratios ofthe obtained materials with the GME topology had a Si/Al ratio around 4to 5 and always higher than 3.5. Other compositions having Si/Al ratiosbelow or above the exemplified examples can also be prepared. Thecorresponding silica/alumina ratios were thus around 8 to 10 and alwayshigher than 7 in these syntheses. To date, commonly reported GMEaluminosilicates have a silica/alumina ratio below 5. The significantdifferences in composition from previously reported GME aluminosilicatesprovide the basis for naming this material as CIT-9. It is expected thatsimple modifications of the described methods will yield GME materialswith even higher Si/Al ratios, as this is usually the case forOSDA-mediated synthesis. CIT-9 was made statically or in a rotatingoven, as evidenced from Entry 1 and 2. CIT-9 was also made from gelswith a Si/Al content of 15 up to 45 (e.g. Entry 3, 4 and 5) and alsowith other FAU. CIT-9 was also made in lower H₂O:Si gels (entry 6). FIG.3 and Table 2 shows the PXRD diffraction pattern of some of the typicalCIT-9 materials made in Table 1. All reflections match with the reportedpatterns for GME by the International Zeolite Association as well asother literature sources.

TABLE 2 PXRD data (2-θ value) for CIT-9 compositions. See FIG. 3.  7.5 ±0.1 11.6 ± 0.1 14.9 ± 0.1 17.9 ± 0.2 19.9 ± 0.1 21.75 ± 0.15 28.1 ± 0.230.1 ± 0.1

Thermogravimetric analysis of a typical air-dry as-made material (FIG. 4) showed that the total weight loss equaled about 20%. The weight lossfraction over 300° C. was attributed to the removal of the SDA and agood measure for the amount of its incorporation. Relative to thezeolite left at 900° C., the included amount of OSDA was found to bearound 14 wt %, pointing to 1.4 OSDA molecules per unit cell.

¹³C CP-MAS NMR was performed (FIG. 5 ) to further verify the OSDA wasincluded in the zeolite. The NMR trace of the occluded carbon in thezeolite matched well with the OSDA standard (liquid dilution in water,measured in ¹³C CP-MAS). The assignments given in FIG. 5 were verifiedby liquid phase ¹³C NMR (not shown).

The CIT-9 material was not stable when calcined at 580° C. It seemed totransform into an AFI type molecular sieve. The instability of GME hasbeen reported previously. To avoid this issue, the OSDA was removed viaan ozone-treatment at 150° C. The materials retained their crystallineGME PXRD patterns as seen in FIG. 6 and FIG. 7 for MDU80 and MDU93respectively.

The as-synthesized CIT-9 could also be calcined in presence of salts, asan alternative to the ozone-treatment for removal of the OSDA andpreservation of the GME structure. An exemplary synthesis includedmixing as-made CIT-9 (MDU80 recipe) with a 2M KCl solution, in a 1:2zeolite:solution ratio. The slurry was then calcined using followingthermal program: heating from room temperature to 90° C. at a rate of0.1° C./min, then to 500° C. at a rate of 0.5° C./min, then isothermalfor 5 h at 500° C. The structural features of GME, as witnessed by theupper trace in PXRD in FIG. 13 , were still present after the treatment.If CIT-9 was calcined without using the salt solution, the PXRD tracechanged in some places and was more resemblant of an AFI topology (seeFIG. 13 , middle trace): compared to GME, at 11.6 degrees 2-theta, areflection disappeared while at 21.1 degrees 2-theta an additionalsignal appears (dotted indication squares). Similar GME preservationresults were obtained with a 1M KCl solution (using a 1:4zeolite:solution ratio) and with 2M NaCl.

After ozone-treatment, the material was easily exchanged followingstate-of-the-art ion exchange protocols, e.g. with ammonium asdemonstrated for MDU80 in FIG. 6 and with potassium, as demonstrated forMDU93 in FIG. 7 . Furthermore, the K⁺-CIT-9 was found to be verythermally stable, due to the stabilizing presence of the K⁺ ions. Thiscan be evidenced from the upper PXRD trace in FIG. 7 , after calcinationat 580° C.

The morphology of the new material was further studied by SEM.Rectangular (coffin-shaped—to needle like) crystals with lengths ofabout 1-3 μm were obtained and observed (see, e.g., FIGS. 8 and 9 ).

The pore volumes of two CIT-9 materials were assessed by measuring theN₂- and Ar-physisorption isotherms after OSDA removal by ozone-treatment(FIG. 10 ). Both MDU53, probed by N₂, and MDU80, probed by Argon, showedpromising sorption capacities. The pore volumes by t-plot analysis onthe adsorption branch were 0.156 cm³/g for MDU53 and 0.151 cm³/g forMDU80. It should be noted that MDU53 had a significant ANA impurity inPXRD (the material after 110 h of synthesis was measured). This densephase however does not possess sorption capacity. These high sorptioncapacities together with the absence of CHA signals in PXRD indicatethat CIT-9 is an aluminosilicate of the GME topology with very littlefaulting and good pore volumes for applications in sorption andcatalysis.

²⁷Al MAS NMR (FIG. 11 ) and ²⁹Si MAS NMR (FIG. 12 ) were both used tofurther corroborate the successful synthesis of the aluminosilicateframework of CIT-9 (both measured on the calcined K-exchanged MDU93sample). The absence of signals at 0 ppm in Al NMR and the presence ofthe large signal at 57 ppm showed that all aluminum was incorporatedtetrahedrally into the framework. The Si NMR shows three characteristicsignals of typical aluminosilicate materials with intermediate Alcontent. The intensities of these resonances at −98 ppm, 105 ppm and 110ppm allow to calculate the Si/Al ratio according to the known formula.This led to a calculated Si/Al value of 3.95, well in accord with theSi/Al ratio of Table 1.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present inventioncontemplates and claims those inventions resulting from the combinationof features of the invention cited herein and those of the cited priorart references which complement the features of the present invention.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis invention.

All of the references cited in this disclosure are incorporated byreference herein in their entireties for all purposes.

What is claimed:
 1. A crystalline microporous aluminosilicatecomposition of GME topology comprising: (a) an oxide of silicon, andoptionally an oxide of germanium; (b) an oxide of aluminum, andoptionally one or more oxides of boron, gallium, hafnium, iron, tin,titanium, indium, vanadium, or zirconium, wherein the molar ratio of themetals of (a) to the metals of (b) is from 4 to 4.2; and whichcrystalline microporous aluminosilcate composition of GME topologyexhibits a powder XRD pattern having peaks having 2-theta values at7.5+0.10, 11.6+0.10, 14.9+0.10, 17.9+0.2°, 19.9+0.1°, 21.75+0.15°,28.1+0.20°, and 30.1+0.10, wherein the crystalline microporousaluminosilicate composition has pores that contain at least one isomerof the quaternary piperidinium cation of Formula (I):

wherein R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together withthe N to which they are bound form a 5 or 6 membered saturated orunsaturated ring; and R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃alkyl, provided at least two of R², R³, R⁴, R⁵, and R⁶ are independentlyC₁₋₃ alkyl; and the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide nitrate, or hydroxide anion.
 2. Thecrystalline microporous aluminosilicate composition of claim 1, thatexhibits one or more of: (a) an XRD diffraction pattern that is the sameas or consistent with any one of those shown in FIG. 3 , FIG. 6 , FIG. 7, or FIG. 13 ; (b) an ²⁹Si MAS spectrum having a plurality of chemicalshifts of about −99.1, −104.9 and −110.5 ppm, downfield of a peakcorresponding to an external standard of tetramethylsilane; (c) an ²⁹SiMAS spectrum that is the same as or consistent with the one shown inFIG. 13 ; (d) an ²⁷Al MAS NMR spectrum that is the same as or consistentwith the one shown in FIG. 11 , or (e) a thermogravimetric analysiscurve that is the same as or consistent with the one in FIG. 4 ; or (f)a ¹³C CP MAS NMR spectrum that is the same as or consistent with the oneshown in FIG. 5 .
 3. The crystalline microporous aluminosilicatecomposition of claim 1, wherein the at least one isomer of thequaternary piperidinium cation of Formula (I) comprises at least oneisomer of the quaternary piperidinium cation of Formula (IA) or (IB):

wherein R², R³, R⁵, and R⁶ are independently C₁₋₃ alkyl.
 4. Thecrystalline microporous aluminosilicate composition of claim 1, whereinthe at least one isomer of the quaternary piperidinium cation of Formula(I) comprises an N,N-dialkyl-2,6-lupetidinium cation orN,N-dialkyl-3,5-lupetidinium cation:


5. The crystalline microporous aluminosilicate composition of claim 1,wherein the at least one isomer of the quaternary piperidinium cation ofFormula (I) comprises cis-N,N-dimethyl-3,5-lupetidinium cation,trans-N,N-dimethyl-3,5-lupetidinium cation,cis-N,N-dimethyl-2,6-lupetidinium cation,trans-N,N-dimethyl-2,6-lupetidinium cation or a combination thereof. 6.The crystalline microporous aluminosilicate composition of claim 1,prepared by a process comprising hydrothermally treating an aqueouscomposition comprising: (a) a source of a silicon oxide, and optionallya source of germanium oxide, or combination thereof, wherein the sourceof silicon oxide is an aluminosilicate, a silicate, a silica hydrogel,amorphous silica, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicate, a silica hydroxide, silicon alkoxide, orcombination thereof; (b) a source of aluminum oxide, and optionally asource of boron oxide, gallium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination or mixture thereof, wherein the source of aluminum oxide isan alkoxide, hydroxide, or oxide of aluminum, a sodium aluminate, analuminum siloxide, an aluminosilicate, or combination thereof; (c) amineralizing agent comprising an aqueous hydroxide; (d) an organicstructure directing agent (OSDA) comprising at least one isomer of thequaternary piperidinium cation of Formula (I):

and (e) water; under conditions to crystallize the crystallinemicroporous solid of GME topology containing the at least one isomer ofthe quaternary piperidinium cation of Formula (I); wherein R^(A) andR^(B) are independently a C₁₋₃ alkyl, or together with the N to whichthey are bound form a 5 or 6 membered saturated or unsaturated ring; andR², R⁴, and R⁶ are H and R³ and R⁵ are cis-positioned C₁₋₃ alkyl;wherein the quaternary piperidinium cation has an associated bromide,chloride, fluoride, iodide nitrate, or hydroxide anion.
 7. Thecrystalline microporous aluminosilicate composition of claim 6, whereinthe OSDA comprises at least one isomer of the quaternary piperidiniumcation of Formula (IB):

wherein R³ and R⁵ are independently C₁₋₃ alkyl.
 8. The crystallinemicroporous aluminosilicate composition of claim 6, wherein thequaternary piperidinium cation of Formula (I) comprises acis-N,N-dialkyl-3,5-lupetidinium cation:


9. The crystalline microporous aluminosilicate composition of claim 6,wherein the quaternary piperidinium cation of Formula (I) comprisescis-N,N-dimethyl-3,5-lupetidinium cation

and the associated anion is hydroxide.